Narrow Results

Heteroleptic porphyrinato/phthalocyaninato rare earth(III) triple-decker compounds M₂(Por)₂(Pc') (1a-4a) and M₂(Por)(Pc')₂ (1c-4c) (M = Eu, Tb; Por = TDOPP, Pc' = OOPc or Por = TpClPP, Pc' = Pc where H₂(TDOPP) = 5,10,15,20-tetrakis(4-n-dodecyloxyphenyl)porphyrin, H₂[OOPc] = 2,3,9,10,16,17,23,24-octakis(n-octyloxy)phthalocyanine, H₂(TpClPP) = 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin, H₂(Pc') = general phthalocyanine, and H₂(Pc) = unsubstituted phthalocyanine) were obtained by the cyclic tetramerization of the corresponding dicyanobenzenes 7 using monoporphyrinato rare earth(III) acetylacetonates M(Por)acac as templates with catalysis by the organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Double-decker complexes M(Por)(Pc') (M = Eu, Tb; Por = TDOPP, Pc' = OOPc or Por = TpClPP, Pc' = Pc) (1b-4b) were isolated as side products. For the purpose of comparative study, homo- and hetero-dinuclear rare earth triple-deckers with one porphyrinato and two phthalocyaninato ligands M₂(Por)(Pc')₂ (1c, 2c) (M = Eu, Tb; Por = TDOPP, Pc' = OOPc) and (Por)M(Pc')M'(Pc')(M ≠ M' = Eu, Tb) (5c, 6c) were also prepared using the raise-by-one-story method. The complexes were characterized by UV-vis, near-IR, IR and mass spectra. The comparison between ¹H NMR spectra of the two series of triple-decker compounds a and c, and also between the substituted phthalocyanine- and unsubstituted phthalocyanine-containing europium triple-deckers, renders it possible to assign the aromatic proton signals unambiguously.